Metal composite powder and method for producing same

ABSTRACT

There is prepared a silver-coated copper powder wherein the surface of a copper powder having an average particle diameter of 0.1 to 100 μm is coated with 5% by weight or more of silver, and the silver-coated copper powder is sprayed into the tail flame region of a thermal plasma to cause silver on the surface of the copper powder to diffuse in the grain boundaries of copper on the inside of the copper powder to produce a metal composite powder wherein the percentage of the area occupied by silver on a cross section of the metal composite powder is 3 to 20%.

BACKGROUND OF THE INVENTION

Field of the invention

The present invention generally relates to a metal composite powder anda method for producing the same. More specifically, the inventionrelates to a metal composite powder for use in a conductive paste or thelike, and a method for producing the same.

Description of the Prior Art

Conventionally, in order to form electrodes and wires of electronicparts by printing methods and so forth, there is used a conductive pasteproduced by mixing a solvent, a resin, a dispersant and so forth in aconductive metal powder, such as silver or copper powder.

However, silver powder is expensive since it is a powder of a noblemetal although it has a very low volume resistivity to be a goodconductive material. On the other hand, copper powder has an inferiorstorage stability (reliability) to that of silver powder since it iseasily oxidized although it has a low volume resistivity to be a goodconductive material.

In order to solve these problems, there is proposed a silver-coatedcopper powder, wherein the surface of copper powder is coated withsilver, as a metal powder for use in a conductive paste (see, e.g.,Japanese Patent Laid Open Nos. 2010-174311 and 2010-077495).

However, in the silver-coated copper powders disclosed in JapanesePatent Laid Open Nos. 2010-174311 and 2010-077495, if there is a portionof the surface of copper which is not coated with silver, oxidationproceeds from the portion, so that the storage stability (reliability)thereof is insufficient.

In particular, since oxygen is easy to diffuse in grain boundaries,oxidation proceeds from the grain boundaries of copper by the diffusion(grain boundary diffusion) of oxygen along the grain boundaries ofcopper.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to eliminate theaforementioned problems and to provide a metal composite powder, whichcontains copper and silver and which is capable of improving the storagestability (reliability) thereof by preventing oxidation from proceedingfrom the grain boundaries of copper, and a method for producing thesame.

In order to accomplish the aforementioned and other objects, theinventors have diligently studied and found that it is possible toproduce a metal composite powder, which is capable of improving thestorage stability (reliability) thereof by preventing oxidation fromproceeding from the grain boundaries of copper, if a silver-coatedcopper powder, wherein the surface of a copper powder is coated withsilver, is sprayed into a tail flame region of a thermal plasma to causesilver on the surface of the copper powder to diffuse in a grainboundary of copper on the inside of the copper powder. Thus, theinventors have made the present invention.

According to the present invention, there is provided a method forproducing a metal composite powder, the method comprising the steps of:preparing a silver coated copper powder wherein the surface of a copperpowder is coated with silver; and spraying the silver-coated copperpowder into a tail flame region of a thermal plasma to cause silver onthe surface of the copper powder to diffuse in a grain boundary ofcopper on the inside of the copper powder.

In this method for producing a metal composite powder, the tail flameregion of the thermal plasma preferably has a temperature of 2000 to5000 K. The copper powder is preferably produced by atomizing. Thecopper powder preferably has an average particle diameter of 0.1 to 100μm. The content of silver with respect to the silver-coated copperpowder is preferably 5% by weight or more.

According to the present invention, there is provided a metal compositepowder comprising: a copper powder; and silver diffusing in a grainboundary of copper on the inside of the copper powder. In this metalcomposite powder, the copper powder preferably has an average particlediameter of 0.1 to 100 μm. The content of silver with respect to themetal composite powder is preferably 5% by weight or more. Thepercentage of an area composite powder is preferably 3 to 20%.

Throughout the specification, the expression “the average particlediameter of a copper powder” means the particle diameter (D₅₀ diameter)corresponding to 50% of accumulation in cumulative distribution of thecopper powder, which is measured by a laser diffraction particle sizeanalyzer.

According to the present invention, it is possible to provide a metalcomposite powder, which contains copper and silver and which is capableof improving the storage stability (reliability) thereof by preventingoxidation from proceeding from the grain boundaries of copper, and amethod for producing the same.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will be understood more fully from the detaileddescription given herebelow and from the accompanying drawings of thepreferred embodiments of the invention. However, the drawings are notintended to imply limitation of the invention to a specific embodiment,but are for explanation and understanding only.

In the drawings:

FIG. 1 is a compositional image in BE (Backscattered Electron) mode(COMPO image) obtained by observing a cross section of a silver-coatedcopper powder, which was obtained in Comparative Example, by means of afield emission scanning electron microscope (FE-SEM);

FIG. 2 is a COMPO image obtained by observing a cross section of a metalcomposite powder, which was obtained in Example, by means of the FE-SEM;

FIG. 3 is a mapping image obtained by observing a cross section of themetal composite powder, which was obtained in Example, by means of anenergy dispersive X-ray spectrometer (EDS) and a field emission Augerelectron spectrometer (FE-AES);

FIG. 4 is a chart showing the measured results in the thermogravimetrydifferential thermal analysis (TG-DTA) of the silver-coated copperpowder obtained in Comparative Example; and

FIG. 5 is a chart showing the measured results in the TG-DTA of themetal composite powder obtained in Example.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In a preferred embodiment of a method for producing a metal compositepowder according to the present invention, a silver-coated copperpowder, wherein the surface of a copper powder is coated with silver, issprayed into a tail flame region of a thermal plasma to cause silver onthe surface of the copper powder to diffuse in the grain boundaries ofcopper on the inside of the copper powder.

Although the copper powder used as a raw material may be produced by thewet reduction method, electrolysis method, vapor phase method or thelike, it is preferably produced by a so-called atomizing method (such asa gas atomizing method or a water atomizing method) for producing a finepowder by rapidly cooling and solidifying copper, which is melted at atemperature of not lower than the melting temperature thereof, bycausing a high-pressure gas or high-pressure water to collide with themelted copper while causing it to drop from the lower portion of atundish. In particular, if the copper powder is produced by a so-calledwater atomizing method for spraying a high-pressure water, it ispossible to obtain a copper powder having a small particle diameter, sothat it is possible to improve the electric conductivity of anelectrically conductive paste due to the increase of the number ofcontact points between the particles of the copper powder when thecopper powder is used for preparing the electrically conductive paste.

The average particle diameter of the copper powder is preferably in therange of from 0.1 μm to 100 μm, more preferably in the range of from 0.5μm to 20 μm, and most preferably in the range of from 1 μm to 10 μm. Ifthe overage particle diameter of the copper powder is less than 0.1 μm,it is not preferable since it has a had influence on the electricconductivity of the silver-coated copper powder. On the other hand, ifthe average particle diameter of the copper exceeds 100 μm, it is notpreferable since it is difficult to form fine wires.

As a method for coating the copper powder with silver, there may be useda method for depositing silver on the surface of the copper powder by asubstitution method utilizing a substitution reaction for substitutingsilver for copper or by a reduction method using a reducing agent. Forexample, there may be used a method for depositing silver on the surfaceof the copper powder while stirring a solution containing the copperpowder and silver ions in a solvent, or a method for depositing silveron the surface of the copper powder while stirring a mixed solution of asolution containing the copper powder and an organic matter in a solventand a solution containing silver ions and an organic matter in asolvent.

As the solvent, there may be used water, an organic solvent or a mixedsolvent thereof. If a solvent prepared by mixing water with an organicsolvent is used, it is required to use an organic solvent which isliquid at room temperature (20 to 30° C.), and the mixing ratio of waterto the organic solvent may be suitably adjusted in accordance with theused organic solvent. As water used as the solvent, there may be useddistilled water, ion-exchanged water, industrial water or the likeunless there is the possibility that impurities are mixed therein.

As raw materials of silver, silver nitrate having a high solubility withrespect to water and many organic solvents is preferably used since itis required to cause silver ions to exist in a solution. In order tocarry out a reaction for coating the copper powder with silver (silvercoating reaction) as uniform as possible, a silver nitrate solution,which is prepared by dissolving silver nitrate in a solvent (water, anorganic solvent or a mixed solvent thereof), not solid silver nitrate,is preferably used. The amount of the used silver nitrate solution, theconcentration of silver nitrate in the silver nitrate solution, and theamount of the organic solvent may be determined in accordance with theamount of the intended silver containing layer.

In order to more uniformly form silver, a chelating agent may be addedto the solution. As the chelating agent, there is preferably used achelating agent having a high complex stabilization constant withrespect to copper ions and so forth, so as to prevent thereprecipitation of copper ions and so forth, which are formed asvice-generative products by a substitution reaction for substitutingsilver ions for metallic copper. In particular, the chelating agent ispreferably selected in view of the complex stabilization constant withrespect to copper since the copper powder serving as the core of thesilver-coated copper powder contains copper as a main compositionelement. Specifically, as the chelating agent, there may be used achelating agent selected from the group consisting ofethylene-diamine-tetraacetic acid (EDTA), iminodiacetic acid,diethylene-triamine, triethylene-diamine, and salts thereof.

In order to stably and safely carry out the silver coating reaction, abuffer for pH may be added to the solution. As the buffer for pH, theremay be used ammonium carbonate, ammonium hydrogen carbonate, ammoniawater, sodium hydrogen carbonate or the like.

When the silver coating reaction is carried out, a solution containing asilver salt is preferably added to a solution in which the copper powderis sufficiently dispersed by stirring the solution after the copperpowder is put therein before the silver salt is added thereto. Thereaction temperature in the silver coating reaction may be a temperatureat which the solidification or evaporation of the reaction solution isnot caused. The reaction temperature is set to be preferably 10 to 40°C. and more preferably 15 to 35° C. The reaction time may be set in therange of from 1 minute to 5 hours although it varies in accordance withthe amount of the coating silver and the reaction temperature.

The content (coating amount) of silver with respect to the silver-coatedcopper powder is preferably 5% by weight or more, more preferably in therange of from 7% by weight to 50% by weight, more preferably in therange of from 8% by weight to 40% by weight, and most preferably in therange of from 9% by weight to 20% by weight. If the content of silver isless than 5% by weight, it is not preferable since it has a badinfluence on the electric conductivity of the silver-coated copperpowder. On the other hand, if the content of silver exceeds 50% byweight, it is not preferable since the costs thereof are high due to theincrease of the amount of silver to be used.

The silver coated copper powder thus obtained is sprayed into the tailflame region of a thermal plasma to be heat-treated to cause silver onthe surface of the copper powder to diffuse in the grain boundaries ofcopper on the inside of the copper powder. Since plasma flames use cleangases, there is no possibility that impurities are adhered to thesilver-coated copper powder sprayed into the tail flame of the thermalplasma. The period of time for applying heat to the silver-coated copperpowder by the tail flame region of the thermal plasma is a short periodof time, so that it is possible to prevent the aggregation of thesilver-coated copper powder.

In a typical method for utilizing a thermal plasma to produce ultrafineparticles (nanoparticles) by feeding a raw material directly into aplasma flame, the raw material is instantly heated to thousands degreesCelsius in a high temperature region of not less than 10,000° C. of theplasma flame to be decomposed to atoms and/or radicals to be rapidlycooled to about 1,000° C., at which a homogeneous nucleation occurs, ina downstream low-temperature region to synthesize ultrafine particles.However, in the preferred embodiment of a method for producing a metalcomposite powder according to the present invention, the silver-coatedcopper powder is fed into the plasma tail flame region having atemperature of 2000 to 5000 K, so that silver having a lower meltingpoint than that of copper is melted to diffuse while the silver--coatedcopper powder is caused to pass through the plasma tail flame region ina very short period of time. Therefore, it is possible to cause silveron the surface of the copper powder to diffuse in the grain boundariesof copper on the inside of the copper powder while the shape of thecopper powder serving as the core of the silver-coated copper powder ismaintained to some extent. Furthermore, silver on the surface of thecopper powder is preferably caused to diffuse in the grain boundaries ofcopper on the inside of the copper powder to one-third or more theparticle diameter of the copper powder from the surface of the copperpowder, and more preferably caused to diffuse in the whole grainboundaries of copper on the inside of the copper powder.

The spraying of the silver-coated copper powder into the tail flameregion of the thermal plasma may be carried out by means of a thermalplasma apparatus. In order to feed the silver-coated copper powder intothe tail flame region of the thermal plasma having a temperature of 2000to 5000 K by means of the thermal plasma apparatus, the output of theplasma apparatus is preferably 2 to 10 kW, more preferably 4 to 8 kW,and most preferably 5 to 7 kW. The flow rate of argon gas for plasma ispreferably 5 to 40 L/min, and more preferably 15 to 25 L/min. The flowrate of carrier nitrogen gas for supplying the silver-coated copperpowder is preferably 0 to 3 L/min, and more preferably 0 to 0.5 L/min.The pressure in the apparatus is preferably 0 to 100 kPa, and morepreferably 50 to 100 kPa. The amount of the silver-coated copper powderto be supplied is preferably 0.1 to 400 g/min, and more preferably 100to 400 g/min.

In the above-described preferred embodiment of a method for producing ametal composite powder according to the present invention, it ispossible to produce a metal composite powder wherein silver diffuses inthe grain boundaries of copper on the inside of a copper powder. Thecontent of silver with respect to the metal composite powder may be 5%by weight or more (preferably 7 to 50% by weight, more preferably 8 to40% by weight, and most preferably 9 to 20% by weight). The percentageof an area occupied by silver on a cross section of the metal compositepowder may be 3 to 20% (preferably 8 to 20%).

In the grain boundaries, the arrangement of crystals falls intodisorder, and oxygen is easy to diffuse, so that oxidation proceeds fromthe grain boundaries of copper by the diffusion (grain boundarydiffusion) of oxygen along the grain boundaries of copper. However, themetal composite powder according to the present invention, silver iscaused to diffuse in the grain boundaries of copper on the inside of thecopper powder to be filled in the grain boundaries of copper on insideof the copper powder. Therefore, it is possible to suppress oxidationfrom the grain boundaries of copper, so that it is possible to provide ametal composite powder having a high oxidation resistance.

Examples of a metal composite powder and a method for producing the sameaccording to the present invention will be described below in detail.

COMPARATIVE EXAMPLE

There was prepared a commercially available copper powder produced byatomizing (spherical atomized copper powder produced by Nippon AtomizedMetal Powders Corporation, the copper powder having a purity of 99.9% byweight and an average particle diameter of 5 μm).

There were also prepared a solution (solution 1) obtained by dissolving2.6 kg of ammonium carbonate in 450 kg of pure water, and a solution(solution 2) obtained by adding 92 kg of an aqueous silver nitratesolution containing 16.904 kg of silver to a solution obtained bydissolving 319 kg of EDTA-4Na (43%) and 76 kg of ammonium carbonate in284 kg of pure water.

Then, in the atmosphere of nitrogen, 100 kg of the above-describedcopper powder was added to the solution 1, and the temperature of thesolution was raised to 35° C. while stirring the solution. Then, thesolution 2 was added to the solution containing copper dispersedtherein, and was stirred for 30 minutes.

Thereafter, a solid content obtained by filtration was washed withion-exchanged water until a transparent filtrate was obtained, and then,the washed solid content was vacuum-dried at 70° C. to obtain a copperpowder coated with silver (a silver-coated copper powder).

After a cross section of the silver-coated copper powder thus obtainedwas produced by a cross section polisher (CP), the cross section wasobserved by means of a field emission scanning electron microscope(FE-SEM). The compositional image in BE mode (COMPO image) of the crosssection of the silver-coated copper powder in this observation shown inFIG. 1. In this COMPO image, since brightness is lighter as atomicweight is larger, silver appears to be lighter than copper, so that therelatively light portion of brightness corresponds to silver and thedark portion thereof corresponds to copper. It can be seen from theCOMPO image that the copper powder is coated with silver in thesilver-coated copper powder obtained in this comparative example.Furthermore, the black lines observed on the inside of the copper powderserving as the core of the silver-coated copper powder show the grainboundaries of copper.

Then, a thermogravimetry/differential thermal analyzer (TG-DTAapparatus) (Thermo Plus EVO2 TG-8120 produced by Rigaku Co., Ltd.) wasused for carrying out the TG-DTA measurement of 40 mg of thesilver-coated copper powder, which was distributed from the obtainedsilver-coated copper powder, by raising the temperature thereof at arate of temperature increase of 10° C./min from room temperature (25°C.) to 400° C. while causing air to flow at a flow rate of 200 mL/mintherein. The measured results thereof are shown in FIG. 4. On the basisof a rate (%) of weight increase obtained from a difference (the weightincreased by heating) between each of weights of the silver-coatedcopper powder obtained at temperatures of 200° C., 250° C., 300° C.,350° C. and 400° C. in this measurement and the weight of thesilver-coated copper powder before heating, with respect to the weightof the silver-coated copper powder before heating, the storage stability(reliability) of the silver-coated copper powder was evaluated byevaluating the high-temperature stability (with respect to oxidation) ofthe silver-coated copper powder in air, assuming that all of the weightsincreased by heating were weights increased by oxidation of thesilver-coated copper powder. As result, the rates of weight increase at200° C., 250° C., 300° C., 350° C. and 400° C. were 0.16%, 0.46%, 1.27%,3.80% and 6.54%, respectively. In the TG-DTA measurement of thesilver-coated copper powder obtained in this comparative example, anexothermic peak (with increase in weight due to oxidation) appeared.

The COMPO image of the cross section of the silver-coated copper powdershown in FIG. 1 and a particle analyzing software (Region Adviserproduced by SYSTEM IN FRONTIER INC.) were used for carrying out theimage analysis of the cross section of the silver-coated copper powderin this comparative example. In this image analysis, after the datesmoothing of the COMPO image was carried out, the contrast thereof wasset to be 100 and the brightness thereof was controlled between 60 and100 in an automatic contrast/brightness controlling portion (ACB), and abinary coded processing in a histogram system (a processing forconstructing a histogram of brightness values on the image to binarizethe image on the basis of the tendency of the histogram) was carried outby a region segmentation. As a result, the percentage of silver withrespect to the whole cross-sectional area of the silver--coated copperpowder (the amount of silver on the cross section) was 3.85% which wassmaller than the content of silver (11.06%). Furthermore, the content ofsilver in the silver-coated copper powder in this comparative examplewas obtained as follows. First, 5.0 g of the silver-coated copper powderwas added to 40 mL of an aqueous nitric acid solution prepared bydiluting an aqueous nitric acid solution having a specific gravity of1.38 with pure water at a volume ratio of 1:1, and the solution wasboiled by a heater to completely dissolve the silver-coated copperpowder therein. Thereafter, an aqueous hydrochloric acid solutionprepared by diluting an aqueous hydrochloric acid solution having aspecific gravity of 1.18 with pure water at a volume ratio of 1:1 wasadded to the above-described aqueous solution, in which thesilver-coated copper powder was completely dissolved, little by littleto deposit silver chloride, and the aqueous hydrochloric acid solutionwas added until no precipitates of silver chloride were produced. Thecontent of silver was calculated from the weight of obtained silverchloride to obtain the content of silver in the silver-coated copperpowder.

EXAMPLE

The silver-coated copper powder obtained in the comparative example wassprayed into the tail flame region of a thermal plasma by means ofthermal plasma apparatus (Nanoparticle Synthesis Experimental Apparatusproduced by JEOL Ltd.) to be heat-treated to obtain a metal compositepowder. This plasma tail flame region was purple, so that it can bedetermined that the temperature thereof was 3000 to 5000 K. In thisprocess, the output of the thermal plasma apparatus was 6 kW. The flowrate of argon gas for plasma was 20 L/min, and the flow rate of carriernitrogen gas for supplying the silver-coated copper powder was 2 L/min.The pressure in the apparatus was 50 kPa, and the amount of thesilver-coated copper powder to be supplied was 2.5 g/min.

After a cross section of the metal composite powder thus obtained wasproduced by the cross section polisher (CP), the cross section wasobserved by means of the field emission scanning electron microscope(FE-SEM). The COMPO image of the cross section of the metal compositepowder in this observation is shown in FIG. 2. It can be seen from thisCOMPO image that silver is caused to diffuse in the whole grainboundaries of copper on the inside of the copper powder although thesurface of the copper powder is not coated with silver, in the metalcomposite powder obtained in this example.

Then, the cross section of the metal composite powder obtained in thisexample was observed by means of an energy dispersive X-ray spectrometer(EDS) and a field emission Auger electron spectrometer (FE-AES). Themapping image of the cross section of the metal composite powder in thisobservation is shown in FIG. 3. It can be also seen from this mappingimage that silver is caused to diffuse in the grain boundaries ofcopper.

With respect to the obtained metal composite powder, the TG-DTAmeasurement was carried out by the same method as that in thecomparative example. The measured results thereof are shown in FIG. 5.On the basis of a rate (%) of weight increase obtained from a difference(the weight increased by heating) between each of weights of the metalcomposite powder obtained at temperatures of 200° C., 250° C., 300° C.,350° C. and 400° C. in this measurement and the weight of the metalcomposite powder before heating, with respect to the weight of the metalcomposite powder before heating, the storage stability (reliability) ofthe metal composite powder was evaluated by evaluating thehigh-temperature stability (with respect to oxidation) of the metalcomposite powder in air, assuming that all of the weights increased byheating were weights increased by oxidation of the metal compositepowder. As a result, the rates of weight increase at 200° C., 250° C.,300° C., 350° C. and 400° C. were 0.42%, 0.73%, 1.38%, 2.44% and 3.99%,respectively. It can be seen from these results that thehigh-temperature stability (with respect to oxidation) of the metalcomposite powder in air is improved, so that the storage stability(reliability) of the metal composite powder is improved, since the ratesof weight increase at high temperatures in the metal composite powderobtained in this example are smaller than those in the silver-coatedcopper powder obtained in the comparative example. Furthermore, in theTG-DTA measurement of the metal composite powder obtained in thisexample, no exothermic peak (with increase in weight due to oxidation)appeared.

The COMPO image of the cross section of the metal composite powder shownin FIG. 2 and the particle analyzing software (Region Adviser producedby SYSTEM IN FRONTIER INC.) were used for carrying out the imageanalysis of the cross section of the metal composite powder in thisexample. As a result, the percentage of silver with respect to the wholecross-sectional area of the metal composite powder (the amount of silveron the cross section) was 12.00% which was larger than the content ofsilver (10.92%). Furthermore, the content of silver in the metalcomposite powder in this example was obtained as follows. First, 5.0 gof the metal composite powder was added to 5 mL of an aqueous nitricacid solution prepared by diluting an aqueous nitric acid solutionhaving a specific gravity of 1.38 with pure water at a volume ratio of1:1, and the solution was boiled by a heater to completely dissolve themetal composite powder therein. Thereafter, a filtrate obtained byfiltration was caused to have a constant volume by adding pure waterthereto, and the content of silver in the metal composite powder wasobtained by quantitative analysis by means of an inductively coupledplasma (ICP) emission spectrophotometric analyzer (iCAP 6300 produced byThermo Scientific).

While the present invention has been disclosed in terms of the preferredembodiment in order to facilitate better understanding thereof, itshould be appreciated that the invention can be embodied in various wayswithout departing from the principle of the invention. Therefore, theinvention should be understood to include all possible embodiments andmodification to the shown embodiments which can be embodied withoutdeparting from the principle of the invention as set forth in theappended claims.

What is claimed is:
 1. A method for producing a metal composite powder,the method comprising the steps of: preparing a silver-coated copperpowder wherein the surface of a copper powder is coated with silver; andspraying the silver-coated copper powder into a tail flame region of athermal plasma to cause silver on the surface of the copper powder todiffuse in a grain boundary of copper on the inside of the copperpowder.
 2. A method for producing a metal composite powder as set forthin claim 1, wherein said tail flame region of the thermal plasma has atemperature of 2000 to 5000 K.
 3. A method for producing a metalcomposite powder as set forth in claim 1, wherein said copper powder isproduced by atomizing.
 4. A method for producing a metal compositepowder as set forth in claim 1, wherein said copper powder has anaverage particle diameter of 0.1 to 100 μm.
 5. A method for producing ametal composite powder as set forth in claim 1, wherein the content ofsilver with respect to said silver-coated copper powder is not less than5% by weight.
 6. A metal composite powder comprising: a copper powder;and silver diffusing in a grain boundary of copper on the inside of thecopper powder.
 7. A metal composite powder as set forth in claim 6,wherein said copper powder has an average particle diameter of 0.1 to100 μm.
 8. A metal composite powder as set forth in claim 6, wherein thecontent of silver with respect to said metal composite powder is notless than 5% by weight.
 9. A metal composite powder as set forth inclaim 6, wherein the percentage of an area occupied by silver on a crosssection of said metal composite powder is 3 to 20%.